CN115559061A - 一种高性能pe纤维复合无纬布及其生产工艺 - Google Patents

一种高性能pe纤维复合无纬布及其生产工艺 Download PDF

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CN115559061A
CN115559061A CN202211209750.0A CN202211209750A CN115559061A CN 115559061 A CN115559061 A CN 115559061A CN 202211209750 A CN202211209750 A CN 202211209750A CN 115559061 A CN115559061 A CN 115559061A
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杨燕芳
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Chongqing Meilisi New Material Technology Co ltd
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Abstract

本发明涉及一种高性能PE纤维复合无纬布及其生产工艺，属于特种复合材料技术领域。该无纬布由表面改性PE纤维与粘结剂压合而成，粘结剂包括低聚环氧树脂和其质量2.8％的固化剂。该低聚环氧树脂由双酚A和4,4'‑二氯二苯基亚砜嵌段共聚，再以丙三醇三缩水甘油醚环氧化改性，粘结强度高、化学交联性高；表面改性PE纤维以UHMWPE原丝为原料，经过氧化、酰氯化处理，提高表面活性，再由KH550接枝上硅氧烷基团，提高纤维与粘结剂的相容性，水解后与低聚环氧树脂交联，提高粘结剂与纤维的结合强度，片材受到冲击，排布的纤维不易脱粘滑移，从而具有良好的防弹性能。

Description

一种高性能PE纤维复合无纬布及其生产工艺
技术领域
本发明属于特种复合材料技术领域，具体地，涉及一种高性能PE纤维复合无纬布及其生产工艺。
背景技术
高强高模量聚乙烯纤维(UHMWPE)是继碳酸酯纤维和芳纶纤维之后出现的第三代高性能纤维，其除了具有高强度和比模量外，还具有良好的刚性、耐磨性、耐冲击性、耐化学品、不吸水等优良特性，主要被用于特种防护材料，如防弹衣、防弹头盔、特种绳索等。
UHMWPE纤维或者束丝并不能起到防弹作用，需要将其制成无纬布的形式才具有良好的防弹性能，所谓无纬布是将UHMWPE纤维均匀铺丝，再通过粘结剂粘接成片材，再将片材正交压成没有交织点的布料，这种材料在受到子弹冲击时，大部分冲击动能通过冲击点或冲击点附近的纤维伸长断裂被吸收，其单向排列且充分伸展的纤维使受到冲击的能量向外传播更快，从而有良好的防弹性能。
UHMWPE纤维的化学组成中含有大量的亚甲基基团，非极性的性质使得其与粘结剂之间难以润湿，且不易与粘结剂键合，使得现有的粘结剂与纤维的粘结强度不高，在受到子弹冲击时，排布的纤维易脱粘滑移，产生撕裂，从而防弹性能大打折扣；因此，本申请旨在提高UHMWPE纤维和粘结剂的粘结强度，提高无纬布的性能。
发明内容
为了解决背景技术中提到的技术问题，本发明的目的在于提供一种高性能PE纤维复合无纬布及其生产工艺。
本发明的目的可以通过以下技术方案实现：
一种高性能PE纤维复合无纬布，由表面改性PE纤维与粘结剂压合而成，其中，粘结剂包括：低聚环氧树脂和其质量2.8％的固化剂。
所述低聚环氧树脂由以下方法制备：
步骤A1：将双酚A、4,4'-二氯二苯基亚砜和N-甲基吡咯烷酮在氮气保护下预升温至120℃搅拌溶解，之后设置搅拌速率为600rpm，向反应液中通入热氨气，并升温至172-178℃搅拌反应45-52min，反应结束投加无氧水混合洗涤，分离出洗涤水，制得低聚基体；
进一步的，双酚A、4,4'-二氯二苯基亚砜和N-甲基吡咯烷酮的用量比为0.11mol：0.1mol：320mL。
进一步地，热氨气的通气比为0.18-0.22vvm，热氨气的温度不低于110℃。
步骤A2：将低聚基体、丙三醇三缩水甘油醚和DMF在氮气保护下搅拌溶解，再加入氢氧化钾的乙醇溶解液混合，升温至125-135℃回流反应2-3h，反应结束趁热投加片碱，冷却至室温过滤出片碱，加入丙酮旋蒸带出DMF，制得低聚环氧树脂。
进一步地，低聚基体中的羟基和丙三醇三缩水甘油醚的环氧基的摩尔比为1:3。
所述表面改性PE纤维由以下方法制备：
步骤B1：将浓硫酸与饱和高锰酸钾溶液混合作为氧化液，再将UHMWPE原丝浸入氧化液中，升温至65℃保温2h，取出沥干后用水清洗数次，制得表面氧化纤维；
进一步地，氧化液中浓硫酸与饱和高锰酸钾溶液的用量体积比为10:1。
步骤B2：将氯化亚砜、苯和DMF混合作为活化液，再将表面氧化纤维浸入活化液，升温至40℃保温5h，取出沥干后用无水乙醇清洗数次，制得表面活化纤维；
进一步地，活化液中氯化亚砜、苯和DMF的用量体积比为2:1:0.05。
步骤B3：将KH550、氢氧化钠和无水乙醇混合溶解作为改性液，再将表面活化纤维浸入改性液，室温下浸泡12h，取出沥干即制得表面改性PE纤维。
进一步地，改性液中KH550、氢氧化钠和无水乙醇的用量比为1mL：2mg：5mL。
一种高性能PE纤维复合无纬布的生产工艺，具体包括以下工序：
工序S1：将低聚环氧树脂和固化剂高速搅拌混合、真空脱泡，得到粘结剂；
工序S2：将表面改性PE纤维浸入体积浓度为30％的碱性乙醇溶液，升温至60℃漂洗30min，使得表面接枝的硅氧烷水解为硅醇，取出沥干、辊涂粘结剂、铺丝、裁剪，得到丝片；
工序S3：将丝片正交叠铺，置于热压机中，温度为90℃，压力为1.3MPa，持压时间为3min，冷却后制成高性能PE纤维复合无纬布。
进一步地，固化剂选自中温固化剂DMP-30。
进一步地，粘结剂的辊涂量为1.2g/cm2。
本发明的有益效果：
1.本发明制备一种低聚环氧树脂，以双酚A和4,4'-二氯二苯基亚砜为原料嵌段共聚，通过4,4'-二氯二苯基亚砜共聚改善制成的粘结剂固化后的强度和韧性，通过过量的双酚A对低聚物以高活性的酚羟基封端，保证低聚物的化学活性，之后通过丙三醇三缩水甘油醚改性，在向低聚基体端部接枝上支状环氧基团，制成环氧树脂类粘结剂，本身粘结强度高，且化学交联活性高。
2.本发明提供一种UHMWPE原丝的表面改性方法，先通过浓硫酸和饱和高锰酸钾溶液进行氧化，在表面形成大量含氧基团，再利用氯化亚砜对其酰氯化改性，最后利用KH550与酰氯基团取代反应，在纤维表面接枝上硅氧烷基团，提高纤维与粘结剂的相容性，同时，接枝的硅氧烷配合漂洗工艺发生水解，水解而成的硅醇自身之间可发生缩合，硅醇与制备的低聚环氧树脂交联，从而提高粘结剂与纤维的结合强度，片材受到冲击，排布的纤维不易脱粘滑移，从而具有良好的防弹性能。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例描述所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例8的弹孔冲击形貌图；
图2为本发明对比例1的弹孔冲击形貌图；
图3为本发明对比例2弹孔冲击形貌图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
实施例1
本实施例制备低聚环氧树脂，具体实施过程如下：
a1、取反应釜通入氮气排出空气，处于氮气保护氛围，投加双酚A、4,4'-二氯二苯基亚砜和N-甲基吡咯烷酮，预先升温至120℃并辅以搅拌，将原料搅拌溶解并充分混合，之后设置搅拌速率为600rpm，通过曝气管向反应液中以0.18vvm的通气比通入预热至110℃的氨气，防止反应体系的温度严重下降，同时对反应釜快速升温，直至温度达到172℃，保温搅拌反应52min，双酚A和4,4'-二氯二苯基亚砜聚合形成嵌段共聚物，通过引入4,4'-二氯二苯基亚砜共聚改善制成的粘结剂固化后的强度和韧性，反应结束投加反应液1.2倍的无氧水洗涤，分离出洗涤水，得到低聚基体，在以上反应中，双酚A、4,4'-二氯二苯基亚砜和N-甲基吡咯烷酮的用量比为0.11mol：0.1mol：320mL，过量的双酚A保证低聚物以高活性的酚羟基封端。
a2、取反应釜通入氮气排出空气，处于氮气保护氛围，投加低聚基体和丙三醇三缩水甘油醚混合，加入DMF搅拌溶解，再将氢氧化钾溶解于乙醇溶液后投加到反应釜内混合，升温至125℃回流反应3h，丙三醇三缩水甘油醚中的与低聚基体端部的酚羟基反应，向低聚基体端部接枝上支状环氧基团，反应结束趁热投加片碱，避免反应过程中支状的环氧基开环，冷却至室温过滤出片碱，再投加丙酮旋蒸带出DMF，得到低聚环氧树脂，在以上反应中，投料前检测低聚基体的羟值，控制低聚基体中的羟基和丙三醇三缩水甘油醚的环氧基的摩尔比为1:3，氢氧化钾的用量为底物的0.5％，片碱与反应液的用量比例为2.5g/L。
实施例2
本实施例制备低聚环氧树脂，具体实施过程如下：
a1、取反应釜通入氮气排出空气，处于氮气保护氛围，投加双酚A、4,4'-二氯二苯基亚砜和N-甲基吡咯烷酮，预先升温至120℃并辅以搅拌，将原料搅拌溶解并充分混合，之后设置搅拌速率为600rpm，通过曝气管向反应液中以0.20vvm的通气比通入预热至110℃的氨气，同时对反应釜快速升温，直至温度达到175℃，保温搅拌反应48min，反应结束投加反应液1.2倍的无氧水洗涤，分离出洗涤水，得到低聚基体，在以上反应中，双酚A、4,4'-二氯二苯基亚砜和N-甲基吡咯烷酮的用量比为0.11mol：0.1mol：320mL。
a2、取反应釜通入氮气排出空气，处于氮气保护氛围，投加低聚基体和丙三醇三缩水甘油醚混合，加入DMF搅拌溶解，再将氢氧化钾溶解于乙醇溶液后投加到反应釜内混合，升温至130℃回流反应2.6h，反应结束趁热投加片碱，冷却至室温过滤出片碱，再投加丙酮旋蒸带出DMF，得到低聚环氧树脂，在以上反应中，投料前检测低聚基体的羟值，控制低聚基体中的羟基和丙三醇三缩水甘油醚的环氧基的摩尔比为1:3，氢氧化钾的用量为底物的0.5％，片碱与反应液的用量比例为2.5g/L。
实施例3
本实施例制备低聚环氧树脂，具体实施过程如下：
a1、取反应釜通入氮气排出空气，处于氮气保护氛围，投加双酚A、4,4'-二氯二苯基亚砜和N-甲基吡咯烷酮，预先升温至120℃并辅以搅拌，将原料搅拌溶解并充分混合，之后设置搅拌速率为600rpm，通过曝气管向反应液中以0.20vvm的通气比通入预热至110℃的氨气，同时对反应釜快速升温，直至温度达到178℃，保温搅拌反应48min，反应结束投加反应液1.2倍的无氧水洗涤，分离出洗涤水，得到低聚基体，在以上反应中，双酚A、4,4'-二氯二苯基亚砜和N-甲基吡咯烷酮的用量比为0.11mol：0.1mol：320mL。
a2、取反应釜通入氮气排出空气，处于氮气保护氛围，投加低聚基体和丙三醇三缩水甘油醚混合，加入DMF搅拌溶解，再将氢氧化钾溶解于乙醇溶液后投加到反应釜内混合，升温至132℃回流反应2.4h，反应结束趁热投加片碱，冷却至室温过滤出片碱，再投加丙酮旋蒸带出DMF，得到低聚环氧树脂，在以上反应中，投料前检测低聚基体的羟值，控制低聚基体中的羟基和丙三醇三缩水甘油醚的环氧基的摩尔比为1:3，氢氧化钾的用量为底物的0.5％，片碱与反应液的用量比例为2.5g/L。
实施例4
本实施例制备低聚环氧树脂，具体实施过程如下：
a1、取反应釜通入氮气排出空气，处于氮气保护氛围，投加双酚A、4,4'-二氯二苯基亚砜和N-甲基吡咯烷酮，预先升温至120℃并辅以搅拌，将原料搅拌溶解并充分混合，之后设置搅拌速率为600rpm，通过曝气管向反应液中以0.22vvm的通气比通入预热至110℃的氨气，同时对反应釜快速升温，直至温度达到178℃，保温搅拌反应45min，反应结束投加反应液1.2倍的无氧水洗涤，分离出洗涤水，得到低聚基体，在以上反应中，双酚A、4,4'-二氯二苯基亚砜和N-甲基吡咯烷酮的用量比为0.11mol：0.1mol：320mL，过量的双酚A保证低聚物以高活性的酚羟基封端。
a2、取反应釜通入氮气排出空气，处于氮气保护氛围，投加低聚基体和丙三醇三缩水甘油醚混合，加入DMF搅拌溶解，再将氢氧化钾溶解于乙醇溶液后投加到反应釜内混合，升温至135℃回流反应2h，反应结束趁热投加片碱，避免反应过程中支状的环氧基开环，冷却至室温过滤出片碱，再投加丙酮旋蒸带出DMF，得到低聚环氧树脂，在以上反应中，投料前检测低聚基体的羟值，控制低聚基体中的羟基和丙三醇三缩水甘油醚的环氧基的摩尔比为1:3，氢氧化钾的用量为底物的0.5％，片碱与反应液的用量比例为2.5g/L。
实施例5
本实施例制备表面改性PE纤维，具体实施过程如下：
b1、按照体积比为10:1取浓硫酸和饱和高锰酸钾溶液，搅拌状态下将浓硫酸加入饱和高锰酸钾溶液中混合，作为氧化液，取UHMWPE原丝浸入氧化液中，升温至65℃保温2h，在氧化液的强氧化作用下，UHMWPE原丝表面产生大量的含氧基团，之后取出氧化处理后的UHMWPE原丝用水清洗两次，去除表面的氧化液，得到表面氧化纤维。
b2、将氯化亚砜、苯和DMF按照体积比为2:1:0.05投加到搅拌器中混合作为活化液，再将表面氧化纤维浸入活化液，升温至40℃保温5h，表面氧化纤维的含氧基团与氯化亚砜酰氯化反应，提高纤维的表面活性，之后取出纤维沥干后用无水乙醇清洗两次，得到表面活化纤维。
b3、将KH550、氢氧化钠和无水乙醇按照用量比为1mL：2mg：5mL投加到搅拌器中混合作为改性液，再将表面活化纤维浸入改性液，室温下浸泡12h，KH550上的氨基与改性得到的酰氯基团取代反应，提高纤维与粘结剂的相容性和化学交联性，取出沥干即得到表面改性PE纤维。
实施例6
本实施例制备高性能PE纤维复合无纬布，具体实施过程如下：
工序S1：将实施例1制备的低聚环氧树脂和其质量2.8％的固化剂(为配合铺丝，选用中温固化剂DMP-30，以下实施例相同)以1200rpm高速搅拌混合10min，真空脱气泡5min，即得到粘结剂。
工序S2：将体积浓度为30％乙醇溶液调节pH值为8.0左右的弱碱性环境，浸入实施例5制备的表面改性PE纤维，升温至60℃漂洗30min，表面改性PE纤维上的硅氧烷水解为硅醇，之后取出沥干，再以1.2g/cm2辊涂粘结剂，通过铺丝机铺丝、裁剪，得到涂覆粘结剂的丝片。
工序S3：将四层丝片正交叠铺，之后置于热压机中，设置热压温度为90℃，热压压力为1.3MPa，持压时间为3min，冷却后得到高性能PE纤维复合无纬布。
实施例7
本实施例与实施例6的实施过程相同，采用实施例2制备的低聚环氧树脂和实施例5制备的表面改性PE纤维。
实施例8
本实施例与实施例6的实施过程相同，采用实施例3制备的低聚环氧树脂和实施例5制备的表面改性PE纤维。
实施例9
本实施例与实施例6的实施过程相同，采用实施例4制备的低聚环氧树脂和实施例5制备的表面改性PE纤维。
对比例1
本对比例与实施例8的实施过程相同，将实施例3制备的低聚环氧树脂替换为市售双酚A型环氧树脂胶粘剂，其余完全相同。
对比例2
本对比例与实施例8的实施过程相同，将实施例5制备的表面改性PE纤维替换为UHMWPE纤维，其余完全相同。
取实施例6-实施例9以及对比例1-对比例2制备的无纬布为靶材，采用54式手枪进行实弹射击测试，测量靶材的凹陷深度以及吸收能，观察靶材的弹孔冲击形貌，具体测试数据如表1所示：
表1
凹陷深度/mm 吸收能/J 弹孔冲击形貌
实施例6 9.5 596.7 均匀类圆形凹坑
实施例7 9.3 605.2 均匀类圆形凹坑
实施例8 8.6 587.5 均匀类圆形凹坑
实施例9 9.1 591.3 均匀类圆形凹坑
对比例1 18.7 594.9 倾斜撕裂凹坑
对比例2 击穿 击穿 大面积撕裂弹孔
由表1数据可知，本发明制备的无纬布可抗54式手枪击穿，凹陷深度为8.6-9.5mm，表现出良好的防弹性能，如图1-图3，从弹孔冲击形貌可以看出，实施例8的射击弹孔呈现均匀类圆形凹坑，纤维和粘结剂无明显剥离，而对比例1虽然未完全击穿，但是无纬布出现明显撕裂，对比例2击穿并出现大面积撕裂。
在说明书的描述中，参考术语“一个实施例”、“示例”、“具体示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上内容仅仅是对本发明的构思所作的举例和说明，所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代，只要不偏离发明的构思或者超越本权利要求书所定义的范围，均应属于本发明的保护范围。

Claims (8)

1.一种高性能PE纤维复合无纬布，由表面改性PE纤维与粘结剂压合而成，其特征在于，粘结剂包括低聚环氧树脂和其质量2.8％的固化剂；
所述低聚环氧树脂由以下方法制备：
步骤A1：将双酚A、4,4'-二氯二苯基亚砜和N-甲基吡咯烷酮在氮气保护下预升温至120℃搅拌溶解，搅拌状态下通入热氨气，升温至172-178℃搅拌反应45-52min，反应结束投加无氧水混合洗涤，分离出洗涤水，制得低聚基体；
步骤A2：将低聚基体、丙三醇三缩水甘油醚和DMF在氮气保护下搅拌溶解，再加入氢氧化钾的乙醇溶解液混合，升温至125-135℃回流反应2-3h，反应结束趁热投加片碱，冷却至室温过滤出片碱，加入丙酮旋蒸带出DMF，制得低聚环氧树脂。
2.根据权利要求1所述的一种高性能PE纤维复合无纬布，其特征在于，双酚A、4,4'-二氯二苯基亚砜和N-甲基吡咯烷酮的用量比为0.11mol：0.1mol：320mL。
3.根据权利要求2所述的一种高性能PE纤维复合无纬布，其特征在于，热氨气的通气比为0.18-0.22vvm，热氨气的温度不低于110℃。
4.根据权利要求2所述的一种高性能PE纤维复合无纬布，其特征在于，低聚基体中的羟基和丙三醇三缩水甘油醚的环氧基的摩尔比为1:3。
5.根据权利要求1所述的一种高性能PE纤维复合无纬布，其特征在于，所述表面改性PE纤维由以下方法制备：
步骤B1：将浓硫酸与饱和高锰酸钾溶液混合作为氧化液，再将UHMWPE原丝浸入氧化液中，升温至65℃保温2h，取出沥干后用水清洗数次，制得表面氧化纤维；
步骤B2：将氯化亚砜、苯和DMF混合作为活化液，再将表面氧化纤维浸入活化液，升温至40℃保温5h，取出沥干后用无水乙醇清洗数次，制得表面活化纤维；
步骤B3：将KH550、氢氧化钠和无水乙醇混合溶解作为改性液，再将表面活化纤维浸入改性液，室温下浸泡12h，取出沥干即制得表面改性PE纤维。
6.根据权利要求5所述的一种高性能PE纤维复合无纬布的生产工艺，其特征在于，具体包括以下工序：
工序S1：将低聚环氧树脂和固化剂高速搅拌混合、真空脱泡，得到粘结剂；
工序S2：将表面改性PE纤维浸入体积浓度为30％的碱性乙醇溶液，升温至60℃漂洗30min，取出沥干、辊涂粘结剂、铺丝、裁剪，得到丝片；
工序S3：将丝片正交叠铺，置于热压机中，温度为90℃，压力为1.3MPa，持压时间为3min，冷却后制成高性能PE纤维复合无纬布。
7.根据权利要求6所述的一种高性能PE纤维复合无纬布的生产工艺，其特征在于，固化剂选自中温固化剂DMP-30。
8.根据权利要求7所述的一种高性能PE纤维复合无纬布的生产工艺，其特征在于，粘结剂的辊涂量为1.2g/cm2。
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